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SEMICONDUCTOR GAS SENSORS This page intentionally left blank Woodhead Publishing Series in Electronic and Optical Materials SEMICONDUCTOR GAS SENSORS Second Edition Edited by RAIVO JAANISO University of Tartu, Tartu, Estonia OOI KIANG TAN Nanyang Technological University, Singapore Woodhead Publishing is an imprint of Elsevier The Officers’ Mess Business Centre, Royston Road, Duxford, CB22 4QH, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States The Boulevard, Langford Lane, Kidlington, OX5 1GB, United Kingdom Copyright © 2020 Elsevier Ltd. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-08-102559-8 For information on all Woodhead Publishing publications visit our website at https://www.elsevier.com/books-and-journals Publisher: Matthew Deans Acquisition Editor: Kayla Dos Santos Editorial Project Manager: Ali Afzal-Khan Production Project Manager: Debasish Ghosh Cover Designer: Matthew Limbert Typeset by TNQ Technologies Contents Contributors xi Part One Basics 1. Fundamentals of semiconductor gas sensors 3 Noboru Yamazoe and Kengo Shimanoe 1.1 Introduction 4 1.2 Classification of semiconductor gas sensors 5 1.3 Resistor-type sensors: empirical aspects 6 1.4 Resistor-type sensors: theoretical aspects 14 1.5 Future trends 34 References 37 2. Conduction mechanism in semiconducting metal oxide sensing films: impact on transduction 39 N. B^arsan, M. Huebner and U. Weimar 2.1 Introduction 39 2.2 General discussion about sensing with semiconducting metal oxide gas sensors 41 2.3 Sensing and transduction for p- and n-type semiconducting metal oxides 47 2.4 Investigation of the conduction mechanism in semiconducting metal oxide sensing layers: studies in working conditions 57 2.5 Conduction mechanism switch for n-type SnO2–based sensors during operation in application-relevant conditions 66 2.6 Conclusion and future trends 67 References 67 3. The effect of electrode-oxide interfaces in gas sensor operation 71 Sung Pil Lee and Chowdhury Shaestagir 3.1 Introduction 72 3.2 Electrode materials for semiconductor gas sensors 74 3.3 Electrode-oxide semiconductor interfaces 95 3.4 Charge carrier transport in the electrode-oxide semiconductor interfaces 104 v j vi Contents 3.5 Gas/solid interactions in the electrode-oxide semiconductor interfaces 119 3.6 Conclusions 124 References 125 4. Introduction to semiconductor gas sensors: a block scheme description 133 Arnaldo D’Amico and Corrado Di Natale 4.1 Introduction 133 4.2 The sensor blocks 135 4.3 Metal oxide semiconductor capacitor: the case of the hydrogen gas sensitivity of Pd-SiO2-Si 142 4.4 Light-addressable potentiometric sensor 144 4.5 Metal oxide semiconductor field-effect transistor 148 4.6 Metal oxide semiconductors 151 4.7 Conclusions 156 References 156 Part Two Materials 5. One- and two-dimensional metal oxide nanostructures for chemical sensing 161 E. Comini and D. Zappa 5.1 Introduction 161 5.2 Deposition techniques 162 5.3 Conductometric sensor 169 5.4 Transduction principles and related novel devices 170 5.5 Conclusion and future trends 174 References 175 6. Hybrid materials with carbon nanotubes for gas sensing 185 Thara Seesaard, Teerakiat Kerdcharoen and Chatchawal Wongchoosuk 6.1 Introduction 186 6.2 Synthesis of carbon nanotube 192 6.3 Preparation of carbon nanotubedmetal oxide sensing films 194 6.4 Sensor assembly 199 6.5 Characterization of carbon nanotube–metal oxide materials 200 6.6 Sensing mechanism of carbon nanotube–metal oxide gas sensors 205 Contents vii 6.7 Fabrication of electrodes and CNT/polymer nanocomposites for textile-based sensors 206 6.8 Sensor assembly for textile-based gas sensors 210 6.9 Characterization of CNT/polymer nanocomposites sensing materials on textile substrate 212 6.10 Sensing mechanism of CNT/polymer nanocomposites sensing materials on fabric substrate 215 6.11 Conclusion 216 Acknowledgments 217 References 217 7. Carbon nanomaterials functionalized with macrocyclic compounds for sensing vapors of aromatic VOCs 223 Pierrick Clément and Eduard Llobet 7.1 Introduction 223 7.2 Cyclodextrins 226 7.3 Calixarenes and derivatives 229 7.4 Deep cavitands 230 7.5 Conclusions 232 Acknowledgments 235 References 235 8. Luminescence probing of surface adsorption processes using InGaN/GaN nanowire heterostructure arrays 239 Konrad Maier, Andreas Helwig, Gerhard Muller€ and Martin Eickhoff 8.1 Adsorptiondkey to understanding semiconductor gas sensors 239 8.2 III-nitrides as an emerging semiconductor technology 243 8.3 Photoluminescent InGaN/GaN nanowire arrays 243 8.4 Optical probing of adsorption processes 245 8.5 Experimental observations of PL response 246 8.6 Analysis of adsorption phenomena 250 8.7 Molecular mechanism of adsorption 261 8.8 Conclusions and outlook 266 References 267 9. Rare earth–doped oxide materials for photoluminescence-based gas sensors 271 V. Kiisk and Raivo Jaaniso 9.1 Introduction 272 3þ 9.2 Sm :TiO2 277 3þ 9.3 Eu :ZrO2 288 viii Contents 3þ 9.4 Tb :CePO4 294 3þ 9.5 Pr :(K0.5Na0.5)NbO3 298 9.6 Conclusion 299 References 300 Part Three Methods and integration 10. Recent progress in silicon carbide field effect gas sensors 309 M. Andersson, A. Lloyd Spetz and D. Puglisi 10.1 Introduction 309 10.2 Background: transduction and sensing mechanisms 312 10.3 Sensing layer development for improved selectivity of SiC gas sensors 327 10.4 Dynamic sensor operation and advanced data evaluation 332 10.5 Applications 335 10.6 Summary 338 Acknowledgments 217 References 339 11. Semiconducting direct thermoelectric gas sensors 347 F. Rettig and R. Moos 11.1 Introduction 347 11.2 Direct thermoelectric gas sensors 353 11.3 Conclusion and future trends 380 References 381 12. Dynamic operation of semiconductor sensors 385 Andreas Schutze€ and Tilman Sauerwald 12.1 Introduction 385 12.2 Dynamic operation of metal oxide semiconductor gas sensors 388 12.3 Dynamic operation of gas-sensitive field-effect transistors 398 12.4 Conclusion and outlook 404 References 408 13. Micromachined semiconductor gas sensors 413 D. Briand and J. Courbat 13.1 Introduction 413 13.2 A brief history of semiconductors as gas-sensitive devices 414 13.3 Microhotplate concept and technologies 416 13.4 Micromachined metal oxide gas sensors 425 Contents ix 13.5 Complementary metal oxide semiconductor–compatible metal oxide gas sensors 437 13.6 Micromachined field-effect gas sensors 442 13.7 Nanostructured gas sensing layers on microhotplates 445 13.8 Semiconductor gas sensors on polymeric foil and their additive manufacturing 450 13.9 Manufacturing, products, and applications 454 13.10 Conclusion 458 References 459 14. Integrated CMOS-based sensors for gas and odor detection 465 P.K. Guha, S. Santra and J.W. Gardner 14.1 Introduction 465 14.2 Microresistive complementary metal oxide semiconductor gas sensors 467 14.3 Microcalorimetric complementary metal oxide semiconductor gas sensor 469 14.4 Sensing materials and their deposition on complementary metal oxide semiconductor gas sensors 472 14.5 Interface circuitry and its integration 475 14.6 Integrated multisensor and sensor array systems 480 14.7 Conclusion and future trends 483 Useful web addresses 485 References 486 Index 489 This page intentionally left blank Contributors M. Andersson Linkoping€ University, Linkoping,€ Sweden N. B^arsan University of Tubingen,€ Tubingen,€ Germany D. Briand Ecole Polytechnique Fédérale de Lausanne, Neuch^atel, Switzerland Pierrick Clément Microsystems Laboratory, Ecole Polytechnique Féderale de Lausanne (EPFL), Lausanne, Switzerland E. Comini Department of Information Engineering, University of Brescia, Brescia, Italy J. Courbat Formely Ecole Polytechnique Fédérale de Lausanne, Neuch^atel, Switzerland Arnaldo D’Amico Department of Electronic Engineering, University of Rome Tor Vergata,